Catalytic reduction of NOx

ABSTRACT

A system for NO x  reduction in combustion gases, especially from diesel engines, incorporates an oxidation catalyst to convert at least a portion of NO to NO 2 , particulate filter, a source of reductant such as NH 3  and an SCR catalyst. Considerable improvements in NO x  conversion are observed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 13/843,870, filed Mar. 15, 2013, which was a continuation of U.S. patent application Ser. No. 13/204,634, filed Aug. 5, 2011, now U.S. Pat. No. 8,480,986, which was a continuation of U.S. patent application Ser. No. 12/380,414, filed Feb. 27, 2009, now U.S. Pat. No. 8,142,747, which was a continuation of U.S. patent application Ser. No. 10/886,778, filed Jul. 8, 2004, now U.S. Pat. No. 7,498,010, which was a divisional application of U.S. patent application Ser. No. 09/601,694, filed Jan. 9, 2001, now U.S. Pat. No. 6,805,849, which was the U.S. National Phase of Int'l Pat. Appl. No. PCT/GB1999/000292, filed Jan. 28, 1999, which claimed the benefit of priority from British Application No. 9802504.2, filed Feb. 6, 1998. These applications, in their entirety, are incorporated herein by reference.

SUMMARY OF THE INVENTION

The present invention concerns improvements in selective catalytic reduction of NO_(x) in waste gas streams such as diesel engine exhausts or other lean exhaust gases such as from gasoline direct injection (GDI).

BACKGROUND OF THE INVENTION

The technique named SCR (Selective Catalytic Reduction) is well established for industrial plant combustion gases, and may be broadly described as passing a hot exhaust gas over a catalyst in the presence of a nitrogenous reductant, especially ammonia or urea. This is effective to reduce the NO_(x) content of the exhaust gases by about 20-25% at about 250° C., or possibly rather higher using a platinum catalyst, although platinum catalysts tend to oxidize NH₃ to NO_(x) during higher temperature operation. We believe that SCR systems have been proposed for NO_(x) reduction for vehicle engine exhausts, especially large or heavy duty diesel engines, but this does require on-board storage of such reductants, and is not believed to have met with commercial acceptability at this time.

We believe that if there could be a significant improvement in performance of SCR systems, they would find wider usage and may be introduced into vehicular applications. It is an aim of the present invention to improve significantly the conversion of NO_(x) in a SCR system, and to improve the control of other pollutants using a SCR system.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph plotting percentage NO_(x) conversion against temperature resulting from Test 1.

FIG. 2 is a graph plotting percentage NO_(x) conversion against temperature resulting from Test 2.

FIG. 3 is a graph plotting percentage NO_(x) conversion against temperature resulting from Test 3.

FIG. 4 is a bar graph showing percentage conversion of pollutants [NO_(x), particulates, hydrocarbons (HC) and carbon monoxide (CO)] resulting from Test 4.

DETAILED DESCRIPTION OF THE INVENTION

Accordingly, the present invention provides an improved SCR catalyst system, comprising in combination and in order, an oxidation catalyst effective to convert NO to NO₂, a particulate filter, a source of reductant fluid and downstream of said source, an SCR catalyst.

The invention further provides an improved method of reducing NO_(x) in gas streams containing NO and particulates comprising passing such gas stream over an oxidation catalyst under conditions effective to convert at least a portion of NO in the gas stream to NO₂, removing at least a portion of said particulates, adding reductant fluid to the gas stream containing enhanced NO₂ to form a gas mixture, and passing the gas mixture over an SCR catalyst.

Although the present invention provides, at least in its preferred embodiments, the opportunity to reduce very significantly the NO_(x) emissions from the lean (high in oxygen) exhaust gases from diesel and similar engines, it is to be noted that the invention also permits very good reductions in the levels of other regulated pollutants, especially hydrocarbons and particulates.

The invention is believed to have particular application to the exhausts from heavy duty diesel engines, especially vehicle engines, e.g., truck or bus engines, but is not to be regarded as being limited thereto. Other applications might be LDD (light duty diesel), GDI, CNG (compressed natural gas) engines, ships or stationary sources. For simplicity, however, the majority of this description concerns such vehicle engines.

We have surprisingly found that a “pre-oxidizing” step, which is not generally considered necessary because of the low content of CO and unburnt fuel in diesel exhausts, is particularly effective in increasing the conversion of NO_(x) to N2 by the SCR system. We also believe that minimizing the levels of hydrocarbons in the gases may assist in the conversion of NO to NO₂. This may be achieved catalytically and/or by engine design or management. Desirably, the NO₂/NO ratio is adjusted according to the present invention to the most beneficial such ratio for the particular SCR catalyst and CO and hydrocarbons are oxidized prior to the SCR catalyst. Thus, our preliminary results indicate that for a transition metal/zeolite SCR catalyst it is desirable to convert all NO to NO₂, whereas for a rare earth-based SCR catalyst, a high ratio is desirable providing there is some NO, and for other transition metal-based catalysts gas mixtures are notably better than either substantially only NO or NO₂. Even more surprisingly, the incorporation of a particulate filter permits still higher conversions of NO_(x).

The oxidation catalyst may be any suitable catalyst, and is generally available to those skilled in art. For example, a Pt catalyst deposited upon a ceramic or metal through-flow honeycomb support is particularly suitable. Suitable catalysts are, e.g., Pt/Al₂O₃ catalysts, containing 1-150 g Pt/ft³ (0.035-5.3 g Pt/liter) catalyst volume depending on the NO₂/NO ratio required. Such catalysts may contain other components providing there is a beneficial effect or at least no significant adverse effect.

The source of reductant fluid conveniently uses existing technology to inject fluid into the gas stream. For example, in the tests for the present invention, a mass controller was used to control supply of compressed NH₃, which was injected through an annular injector ring mounted in the exhaust pipe. The injector ring had a plurality of injection ports arranged around its periphery. A conventional diesel fuel injection system including pump and injector nozzle has been used to inject urea by the present applicants. A stream of compressed air was also injected around the nozzle; this provided good mixing and cooling.

The reductant fluid is suitably NH₃, but other reductant fluids including urea, ammonium carbamate and hydrocarbons including diesel fuel may also be considered. Diesel fuel is, of course, carried on board a diesel-powered vehicle, but diesel fuel itself is a less selective reductant than NH₃ and is presently not preferred.

Suitable SCR catalysts are available in the art and include Cu-based and vanadia-based catalysts. A preferred catalyst at present is a V₂O₅/WO₃/TiO₂ catalyst, supported on a honeycomb through-flow support. Although such a catalyst has shown good performance in the tests described hereafter and is commercially available, we have found that sustained high temperature operation can cause catalyst deactivation. Heavy duty diesel engines, which are almost exclusively turbocharged, can produce exhaust gases at greater than 500° C. under conditions of high load and/or high speed, and such temperatures are sufficient to cause catalyst deactivation.

In one embodiment of the invention, therefore, cooling means is provided upstream of the SCR catalyst. Cooling means may suitably be activated by sensing high catalyst temperatures or by other, less direct, means, such as determining conditions likely to lead to high catalyst temperatures. Suitable cooling means include water injection upstream of the SCR catalyst, or air injection, for example utilizing the engine turbocharger to provide a stream of fresh intake air by-passing the engine. We have observed a loss of activity of the catalyst, however, using water injection, and air injection by modifying the turbocharger leads to higher space velocity over the catalyst which tends to reduce NO conversion. Preferably, the preferred SCR catalyst is maintained at a temperature from 160° C. to 450° C.

We believe that in its presently preferred embodiments, the present invention may depend upon an incomplete conversion of NO to NO₂. Desirably, therefore, the oxidation catalyst, or the oxidation catalyst together with the particulate trap if used, yields a gas stream entering the SCR catalyst having a ratio of NO to NO₂ of from about 4:1 to about 1:3 by volume, for the commercial vanadia-type catalyst. As mentioned above, other SCR catalysts perform better with different NO/NO₂ ratios. We do not believe that it has previously been suggested to adjust the NO/NO₂ ratio in order to improve NO reduction.

The present invention incorporates a particulate trap downstream of the oxidation catalyst. We discovered that soot-type particulates may be removed from a particulate trap by “combustion” at relatively low temperatures in the presence of NO₂. In effect, the incorporation of such a particulate trap serves to clean the exhaust gas of particulates without causing accumulation, with resultant blockage or back-pressure problems, whilst simultaneously reducing a proportion of the NOR. Suitable particulate traps are generally available, and are desirably of the type known as wall-flow filters, generally manufactured from a ceramic, but other designs of particulate trap, including woven knitted or non-woven heat-resistant fabrics, may be used.

It may be desirable to incorporate a clean-up catalyst downstream of the SCR catalyst, to remove any NH₃ or derivatives thereof which could pass through unreacted or as by-products. Suitable clean-up catalysts are available to the skilled person.

A particularly interesting possibility arising from the present invention has especial application to light duty diesel engines (car and utility vehicles) and permits a significant reduction in volume and weight of the exhaust gas after-treatment system, in a suitable engineered system.

EXAMPLES

Several tests have been carried out in making the present invention. These are described below, and are supported by results shown in graphical form in the attached drawings.

A commercial 10 liter turbocharged heavy duty diesel engine on a test-bed was used for all the tests described herein.

Test 1 (Comparative)

A conventional SCR system using a commercial V₂O₅/WO₃/TiO₂ catalyst, was adapted and fitted to the exhaust system of the engine. NH₃ was injected upstream of the SCR catalyst at varying ratios. The NH₃ was supplied from a cylinder of compressed gas and a conventional mass flow controller used to control the flow of NH₃ gas to an experimental injection ring. The injection ring was a 10 cm diameter annular ring provided with 20 small injection ports arranged to inject gas in the direction of the exhaust gas flow. NO_(x) conversions were determined by fitting a NO_(x) analyzer before and after the SCR catalyst and are plotted against exhaust gas temperature in FIG. 1. Temperatures were altered by maintaining the engine speed constant and altering the torque applied.

A number of tests were run at different quantities of NH₃ injection, from 60% to 100% of theoretical, calculated at 1:1 NH₃/NO and 4:3 NH₃/NO₂. It can readily be seen that at low temperatures, corresponding to light load, conversions are about 25%, and the highest conversions require stoichiometric (100%) addition of NH₃ at catalyst temperatures of from 325 to 400° C., and reach about 90%. However, we have determined that at greater than about 70% of stoichiometric NH₃ injection, NH₃ slips through the SCR catalyst unreacted, and can cause further pollution problems.

Test 2 (Comparative)

The test rig was modified by inserting into the exhaust pipe upstream of the NH₃ injection, a commercial platinum oxidation catalyst of 10.5 inch diameter and 6 inch length (26.67 cm diameter and 15.24 cm length) containing log Pt/ft³ (=0.35 g/liter) of catalyst volume. Identical tests were run, and it was observed from the results plotted in FIG. 2, that even at 225° C., the conversion of NO_(x) has increased from 25% to >60%. The greatest conversions were in excess of 95%. No slippage of NH₃ was observed in this test nor in the following test.

Test 3

The test rig was modified further, by inserting a particulate trap before the NH₃ injection point, and the tests run again under the same conditions at 100% NH₃ injection and a space velocity in the range 40,000 to 70,000 hr⁻¹ over the SCR catalyst. The results are plotted and shown in FIG. 3. Surprisingly, there is a dramatic improvement in NO_(x) conversion, to above 90% at 225° C., and reaching 100% at 350° C. Additionally, of course, the particulates, which are the most visible pollutant from diesel engines, are also controlled.

Test 4

An R49 test with 80% NH₃ injection was carried out over a V₂O₅/WO₃/TiO₂ SCR catalyst. This gave 67% particulate, 89% HC and 87% NO_(x) conversion; the results are plotted in FIG. 4.

Additionally tests have been carried out with a different diesel engine, and the excellent results illustrated in Tests 3 and 4 above have been confirmed.

The results have been confirmed also for a non-vanadium SCR catalyst. 

We claim:
 1. A method comprising: (a) passing an exhaust gas from a diesel engine over an oxidation catalyst to provide an adjusted gas stream, the exhaust gas comprising a first content level by volume of NO, a first content level by volume of NO₂, and particulate matter, and the adjusted gas stream comprising a second content level by volume of NO that is lower than the first content level of NO, and a second content level by volume of NO₂; (b) passing the adjusted gas stream through a particulate trap that results in trapping at least a portion of the particulate matter on the particulate trap; (c) combusting a portion of the trapped particulate matter such that there is no significant accumulation of particulate matter in the particulate trap in the presence of the adjusted gas stream at a combustion temperature that is lower than the temperature necessary to combust the trapped particulate matter in the presence of the exhaust gas such that there is no significant accumulation of particulate matter in the particulate trap, to create a further adjusted gas stream comprising a third content level by volume of NO and a third content level by volume of NO₂ that is lower than the second content level of NO₂; (d) injecting a reductant fluid comprising urea into the further adjusted gas stream; (e) mixing the further adjusted gas stream with the injected reductant fluid to form a further adjusted gas stream mixed with reductant fluid; and (f) passing the further adjusted gas stream mixed with reductant fluid over an SCR catalyst to provide a final adjusted gas stream comprising a fourth content level by volume of NO and a fourth content level by volume of NO₂; wherein the second content level of NO₂ is sufficiently higher than the first content level of NO₂ such that when a portion of the second content level of NO₂ in the adjusted gas stream is consumed during the combustion of the at least a portion of the trapped particulate matter, the resulting third content level of NO₂ is still sufficiently high for use with the SCR catalyst to provide the final adjusted gas stream where the total combined volume of the fourth content level of NO and the fourth content level of NO₂ is lower than the total combined volume of the first content level of NO and the first content level of NO₂, and the total combined volume of the fourth content level of NO with the fourth content level of NO₂ is lower relative to the respective total combined volume of NO and NO₂ in a final exhaust stream that would result from carrying out steps (b)-(f) starting with the exhaust gas instead of the adjusted gas stream.
 2. The method of claim 1, wherein the diesel engine is a vehicle engine.
 3. The method of claim 1, wherein the diesel engine is a heavy duty diesel truck engine.
 4. The method of claim 1, wherein the diesel engine is a turbocharged heavy duty diesel truck engine.
 5. The method of claim 4, further comprising cooling the further adjusted gas stream.
 6. The method of claim 5, wherein the further adjusted gas stream is cooled by air supplied by the turbocharger.
 7. The method of claim 1, wherein the oxidation catalyst converts less than all of the NO in the exhaust gas to NO₂.
 8. The method of claim 1, wherein the further adjusted gas stream mixed with reductant fluid is at least 225° C. when passed over the SCR catalyst, and the final adjusted gas stream has more than 90% less NO_(x) content by volume than the exhaust gas.
 9. The method of claim 8, wherein the final gas stream has at least 67% less particulate matter content by volume than the exhaust gas.
 10. A method comprising: (a) passing an exhaust gas from a diesel engine over an oxidation catalyst to provide an adjusted gas stream, the exhaust gas comprising a first content level by volume of NO, a first content level by volume of NO₂, and particulate matter, and the adjusted gas stream comprising a second content level by volume of NO that is lower than the first content level of NO, and a second content level by volume of NO₂; (b) passing the adjusted gas stream through a particulate trap that results in trapping at least a portion of the particulate matter on the particulate trap; (c) combusting a portion of the trapped particulate matter in the presence of the adjusted gas stream to reduce a combustion temperature necessary to stop significant accumulation of particulate matter in the particulate trap relative to the combustion temperature of a portion of the particulate matter in the presence of the exhaust gas necessary to stop significant accumulation of particulate matter in the particulate trap, and to create a further adjusted gas stream comprising a third content level by volume of NO and a third content level by volume of NO₂ that is lower than the second content level of NO₂; (d) injecting a reductant fluid comprising urea into the further adjusted gas stream; (e) mixing the further adjusted gas stream with the injected reductant fluid to form a further adjusted gas stream mixed with reductant fluid; and (f) passing the further adjusted gas stream mixed with reductant fluid over an SCR catalyst to provide a final adjusted gas stream comprising a fourth content level by volume of NO and a fourth content level by volume of NO₂; wherein the second content level of NO₂ is sufficiently higher than the first content level of NO₂ such that when a portion of the second content-level of NO₂ in the adjusted gas stream is consumed during the combustion of the at least a portion of the trapped particulate matter, the resulting third content level of NO₂ is still sufficiently high for use with the SCR catalyst to provide the final adjusted gas stream where the total combined volume of the fourth content level of NO and the fourth content level of NO₂ is lower than the total combined volume of the first content level of NO and the first content level of NO₂, and the total combined volume of the fourth content level of NO and the fourth content level of NO₂ is lower relative to the respective total combined volume of NO and NO₂ in a final exhaust stream that would result from carrying out steps (b)-(f) starting with the exhaust gas instead of the adjusted gas stream.
 11. The method of claim 10, wherein the diesel engine is a vehicle engine.
 12. The method of claim 10, wherein the diesel engine is a heavy duty diesel truck engine.
 13. The method of claim 10, wherein the diesel engine is a turbocharged heavy duty diesel truck engine.
 14. The method of claim 13, further comprising cooling the further adjusted gas stream.
 15. The method of claim 14, wherein the further adjusted gas stream is cooled by air supplied by the turbocharger.
 16. The method of claim 10, wherein the oxidation catalyst converts less than all of the NO in the exhaust gas to NO₂.
 17. The method of claim 13, wherein the further adjusted gas stream mixed with reductant fluid is at least 225° C. when passed over the SCR catalyst, and the final adjusted gas stream has more than 90% less NO_(x) content by volume than the exhaust gas.
 18. The method of claim 17, wherein the final gas stream has at least 67% less particulate matter content by volume than the exhaust gas.
 19. A method comprising: (a) passing an exhaust gas from a diesel engine over an oxidation catalyst to provide an adjusted gas stream, the exhaust gas comprising a first content level by volume of NO, a first content level by volume of NO₂, and particulate matter, and the adjusted gas stream comprising a second content level by volume of NO that is lower than the first content level of NO, and a second content level by volume of NO₂; (b) passing the adjusted gas stream through a particulate trap that results in trapping at least a portion of the particulate matter on the particulate trap; (c) combusting a portion of the trapped particulate matter such that there is no significant accumulation of particulate matter in the particulate trap in the presence of the adjusted gas stream at a combustion temperature that is lower than the temperature necessary to combust the trapped particulate matter in the presence of the exhaust gas such that there is no significant accumulation of particulate matter in the particulate trap, to create a further adjusted gas stream comprising a third content level by volume of NO and a third content level by volume of NO₂ that is lower than the second content level of NO₂; (d) injecting a reductant fluid comprising urea into the further adjusted gas stream; (e) mixing the further adjusted gas stream with the injected reductant fluid to form a further adjusted gas stream mixed with reductant fluid; and (f) passing the further adjusted gas stream mixed with reductant fluid over an SCR catalyst to provide a final adjusted gas stream comprising a fourth content level by volume of NO and a fourth content level by volume of NO₂; wherein the second content level of NO₂ is sufficiently higher than the first content level of NO₂ such that when a portion of the second content-level of NO₂ in the adjusted gas stream is consumed during the combustion of the at least a portion of the trapped particulate matter, the resulting third content level of NO₂ is still sufficiently high for use with the SCR catalyst to provide the final adjusted gas stream where the total combined volume of the fourth content level of NO and the fourth content level of NO₂ is lower than the total combined volume of the first content level of NO and the first content level of NO₂, and the total combined volume of the fourth content level of NO and the fourth content level of NO₂ is lower relative to the respective total combined volume of NO and NO₂ in a final exhaust stream that would result from carrying out steps (b)-(f) starting with the exhaust gas instead of the adjusted gas stream; and wherein the further adjusted gas stream mixed with reductant fluid is at least 225° C. when passed over the SCR catalyst, and the final adjusted gas stream has more than 90% less NO_(x) content by volume and at least 67% less particulate matter content by volume than the exhaust gas.
 20. The method of claim 19, wherein the diesel engine is a vehicle engine.
 21. The method of claim 19, wherein the diesel engine is a heavy duty diesel truck engine.
 22. The method of claim 19, wherein the diesel engine is a turbocharged heavy duty diesel truck engine.
 23. The method of claim 22, further comprising cooling the further adjusted gas stream.
 24. The method of claim 23, wherein the further adjusted gas stream is cooled by air supplied by the turbocharger.
 25. The method of claim 19, wherein the oxidation catalyst converts less than all of the NO in the exhaust gas to NO₂. 